DE4408170A1 - New polymerizable liquid crystalline compounds - Google Patents

New polymerizable liquid crystalline compounds

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Publication number
DE4408170A1
DE4408170A1 DE19944408170 DE4408170A DE4408170A1 DE 4408170 A1 DE4408170 A1 DE 4408170A1 DE 19944408170 DE19944408170 DE 19944408170 DE 4408170 A DE4408170 A DE 4408170A DE 4408170 A1 DE4408170 A1 DE 4408170A1
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Prior art keywords
independently
another
liquid
compounds according
polymerizable
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German (de)
Inventor
Paul Dr Delavier
Karl-Heinz Dr Etzbach
Frank Dr Meyer
Karl Dr Siemensmeyer
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BASF SE
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BASF SE
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Priority to PCT/EP1995/000693 priority patent/WO1995024455A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Abstract

The invention concerns polymerisable, liquid-crystalline compounds of general formula (I) in which the Z radicals, independently of one another, mean a polymerisable group having the structure CH2=CCl-, CH2=C(CH3)- or styryl; the Y radicals, independently of one another, mean a direct bond, -O-, -COO-, -OCO- or -S-; the A radicals, independently of one another, mean a spacer having 5 to 30 carbon atoms in which every third carbon atom can be replaced by 0, S, NH, N(CH3) or COO; R<1>, R<2> and R<3>, independently of one another, mean conventional substituents. The compounds of the invention are suitable, inter alia, for preparing colouring agents ordered as cholesteric liquid crystals.

Description

Wie für formanisotrope Medien bekannt, können beim Erwärmen flüssigkristalline Phasen, sogenannte Mesophasen, auftreten. Die einzelnen Phasen unterscheiden sich durch die räumliche Anordnung der Molekülschwerpunkte einerseits sowie durch die Molekülanord­ nung hinsichtlich der Längsachsen andererseits (G.W. Gray, P. A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974). Die nematisch flüssigkristalline Phase zeichnet sich dadurch aus, daß lediglich eine Orientierungsfern­ ordnung durch Parallellagerung der Moleküllängsachsen existiert. Unter der Voraussetzung, daß die die nematische Phase aufbauenden Moleküle chiral sind, entsteht eine sogenannte cholesterische Phase, bei der die Längsachsen der Moleküle eine zu ihnen senk­ rechte, helixartige Überstruktur ausbilden (H. Baessler, Fest­ körperprobleme XI, 1971). Der chirale Molekülteil kann sowohl im flüssigkristallinen Molekül selbst vorhanden sein als auch als Dotierstoff zur nematischen Phase gegeben werden, wobei die cholesterische Phase induziert wird. Dieses Phänomen wurde zuerst an Cholesterolderivaten untersucht (z. B. H. Baessler, M.M. Labes, J. Chem. Phys., 52, 631 (1970); H. Baessler, T.M. Laronge, M. M. Labes, J. Chem. Phys., 51, 799 (1969); H. Finkelmann, H. Stegemeyer, Z. Naturforschg. 28a, 799 (1973); H. Stegemeyer, K.J. Mainusch, Naturwiss., 58, 599 (1971), H. Finkelmann, H. Stegemeyer, Ber. Bunsenges. Phys. Chem. 78, 869 (1974)).As known for shape anisotropic media, when heated liquid-crystalline phases, so-called mesophases, occur. The individual phases differ in their spatial arrangement the molecular focus on the one hand and by the molecular arrangement on the other hand with regard to the longitudinal axes (G.W. Gray, P. A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974). The nematic liquid crystalline phase is characterized by the fact that only a distant orientation Order exists through parallel storage of the molecular axes. Provided that the building the nematic phase Molecules are chiral, a so-called cholesteric arises Phase in which the longitudinal axes of the molecules lower one towards them form right, helical superstructure (H. Baessler, Fest body problems XI, 1971). The chiral part of the molecule can both to be present in the liquid crystalline molecule itself as well be added as a dopant to the nematic phase, the cholesteric phase is induced. This phenomenon came first on cholesterol derivatives (e.g. H. Baessler, M.M. Labes, J. Chem. Phys., 52, 631 (1970); H. Baessler, T.M. Laronge, M. M. Labes, J. Chem. Phys., 51, 799 (1969); H. Finkelmann, H. Stegemeyer, Z. Naturforschg. 28a, 799 (1973); H. Stegemeyer, K.J. Mainusch, Naturwiss., 58, 599 (1971), H. Finkelmann, H. Stegemeyer, Ber. Bunsenges. Phys. Chem. 78, 869 (1974)).

Die cholesterische Phase hat bemerkenswerte optische Eigen­ schaften: eine hohe optische Rotation sowie einen ausgeprägten Zirkulardichroismus, der durch Selektivreflexion von zirkular polarisiertem Licht innerhalb der cholesterischen Schicht ent­ steht. Die je nach Blickwinkel unterschiedlich erscheinenden Farben sind abhängig von der Ganghöhe der helixartigen Über­ struktur, die ihrerseits vom Verdrillungsvermögen der chiralen Komponente abhängt. Dabei kann insbesondere durch Änderung der Konzentration eines chiralen Dotierstoffes die Ganghöhe und damit der Wellenlängenbereich des selektiv reflektierten Lichtes einer cholesterischen Schicht variiert werden. Solche cholesterischen Systeme bieten für eine praktische Anwendung interessante Möglichkeiten. So kann durch Einbau chiraler Molekülteile in mesogene Acrylsäureester und Orientierung in der cholesterischen Phase, z. B. nach der Photovernetzung, ein stabiles, farbiges Netzwerk hergestellt werden, dessen Konzentration an chiraler Komponente dann aber nicht mehr verändert werden kann (G. Galli, M. Laus, A. Angelon, Makromol. Chemie, 187, 289 (1986)). Durch Zumischen von nichtvernetzbaren chiralen Verbindungen zu nemati­ schen Acrylsäureestern kann durch Photovernetzung ein farbiges Polymer hergestellt werden, welches noch hohe Anteile löslicher Komponenten enthält (I. Heyndricks, D.J. Broer, Mol. Cryst. Liq. Cryst. 203, 113 (1991)). Weiterhin kann durch statistische Hydro­ silylierung von Gemischen aus Cholesterolderivaten und acrylat­ haltigen Mesogenen mit definierten zyklischen Siloxanen und anschließende Photopolymerisation ein cholesterisches Netzwerk gewonnen werden, bei dem die chirale Komponente einen Anteil von bis zu 50% an dem eingesetzten Material haben kann; diese Poly­ merisate enthalten jedoch noch deutliche Mengen löslicher Anteile (F.H. Kreuzer, R. Maurer, Ch. Müller-Rees, J. Stohrer, Vortrag Nr. 7, 22. Freiburger Arbeitstagung Flüssigkristalle, Freiburg, 1993).The cholesteric phase has remarkable optical properties shaft: a high optical rotation as well as a pronounced Circular dichroism by selective reflection from circular polarized light within the cholesteric layer ent stands. Which appear different depending on the perspective Colors depend on the pitch of the helical overlays structure, which in turn depends on the twisting power of the chiral Component depends. In particular, by changing the Concentration of a chiral dopant and therefore the pitch the wavelength range of the selectively reflected light cholesteric layer can be varied. Such cholesteric Systems offer interesting ones for a practical application Options. By incorporating chiral parts of the molecule into mesogenic acrylic acid esters and orientation in the cholesteric Phase, e.g. B. after photocrosslinking, a stable, colored Network are created, its concentration of chiral Component can then no longer be changed (G. Galli, M. Laus, A. Angelon, Makromol. Chemie, 187, 289 (1986)). By  Add non-cross-linkable chiral compounds to nemati Some acrylic acid esters can be colored by photocrosslinking Polymer are produced, which is still highly soluble Components contains (I. Heyndricks, D.J. Broer, Mol. Cryst. Liq. Cryst. 203: 113 (1991)). Furthermore, statistical hydro silylation of mixtures of cholesterol derivatives and acrylate containing mesogens with defined cyclic siloxanes and subsequent photopolymerization a cholesteric network are obtained in which the chiral component has a proportion of can have up to 50% of the material used; this poly However, merisates still contain significant amounts of soluble fractions (F.H. Kreuzer, R. Maurer, Ch. Müller-Rees, J. Stohrer, lecture No. 7, 22nd Freiburg Liquid Crystal Working Conference, Freiburg, 1993).

In der Anmeldung DE-OS-35 35 547 wird ein Verfahren beschrieben, bei dem eine Mischung cholesterolhaltiger Monoacrylate über eine Photovernetzung zu cholesterischen Schichten verarbeitet werden kann. Allerdings beträgt der Gesamtanteil der chiralen Komponente in der Mischung ca. 94%. Als reines Seitenkettenpolymer ist ein solches Material zwar mechanisch nicht sehr stabil, eine Erhöhung der Stabilität kann aber durch hochvernetzende Verdünnungsmittel erreicht werden.In the application DE-OS-35 35 547 a method is described in which a mixture of cholesterol-containing monoacrylates over a Photo crosslinking can be processed into cholesteric layers can. However, the total proportion of the chiral component is in the mixture approx. 94%. As a pure side chain polymer is a such material is not mechanically very stable, an increase however, stability can be achieved through highly cross-linking diluents can be achieved.

Neben oben beschriebenen nematischen und cholesterischen Netz­ werken sind auch smektische Netzwerke bekannt, welche ins­ besondere durch Photopolymerisation/Photovernetzung von smektisch flüssigkristallinen Materialien in der smektisch flüssig­ kristallinen Phase hergestellt werden. Die hierfür verwendeten Materialien sind in der Regel symmetrische, flüssigkristalline Bisacrylate, wie sie z. B. D.J. Broer und R.A.M. Hikmet, Makromol. Chem., 190, 3201-3215 (1989) beschrieben haben. Diese Materialien weisen aber sehr hohe Klärtemperaturen von < 120°C auf, so daß die Gefahr einer thermischen Polymerisation gegeben ist. Durch Zumischen chiraler Materialien können beim Vorliegen einer Sc-Phase piezoelektrische Eigenschaften erzielt werden (R.A.M. Hikmet, Macromolecules 25, S. 5759, 1992).In addition to the nematic and cholesteric networks described above, smectic networks are also known, which are produced in particular by photopolymerization / photocrosslinking of smectically liquid-crystalline materials in the smectically liquid-crystalline phase. The materials used for this are generally symmetrical, liquid-crystalline bisacrylates such as those found in BDJ Broer and RAM Hikmet, Makromol. Chem., 190, 3201-3215 (1989). However, these materials have very high clarification temperatures of <120 ° C., so that there is a risk of thermal polymerization. By adding chiral materials, piezoelectric properties can be achieved in the presence of an S c phase (RAM Hikmet, Macromolecules 25, p. 5759, 1992).

Aufgabe der vorliegenden Erfindung war die Herstellung neuer polymerisierbarer nematisch flüssigkristalliner Materialien, die allein oder in Mischungen mit anderen polymerisierbaren nematischen Flüssigkristallen breite nematische Phasenbereiche und Klärtemperaturen unterhalb 120°C aufweisen oder induzieren und die unterhalb von 120°C verarbeitet werden können. The object of the present invention was to produce new ones polymerizable nematic liquid crystalline materials, the alone or in mixtures with other polymerizable nematic liquid crystals wide nematic phase ranges and have or induce clarification temperatures below 120 ° C and that can be processed below 120 ° C.  

Die Erfindung betrifft daher polymerisierbare, flüssigkristalline Verbindungen der allgemeinen Formel IThe invention therefore relates to polymerizable, liquid-crystalline Compounds of the general formula I

in der die Reste
Z unabhängig voneinander eine polymerisierbare Gruppe der Struktur CH₂=CCl-, CH₂=C(CH₃)- oder Styryl,
Y unabhängig voneinander eine direkte Bindung, -O-, -COO-, -OCO- oder -S-,
A unabhängig voneinander einen Spacer mit 5 bis 30 C-Atomen, in denen jedes dritte C-Atom durch O, S, NH, N(CH₃) oder COO ersetzt sein kann und
R¹, R² und R³ unabhängig voneinander Wasserstoff, C₁- bis C₂₀-Alkyl, C₁- bis C₂₀-Alkoxy, C₁- bis C₂₀-Alkoxy­ carbonyl, C₁- bis C₂₀-Monoalkylaminocarbonyl, Formyl, C₁- bis C₂₀-Alkylcarbonyl, Fluor, Chlor, Brom, Cyan, C₁- bis C₂₀-Alkylcarbonyloxy, C₁- bis C₂₀-Alkylcarbo­ nylamino, Hydroxy oder Nitro bedeuten.in which the leftovers
Z independently of one another is a polymerizable group of the structure CH₂ = CCl-, CH₂ = C (CH₃) - or styryl,
Y independently of one another is a direct bond, -O-, -COO-, -OCO- or -S-,
A independently of one another a spacer with 5 to 30 carbon atoms, in which every third carbon atom can be replaced by O, S, NH, N (CH₃) or COO and
R¹, R² and R³ independently of one another hydrogen, C₁- to C₂₀-alkyl, C₁- to C₂₀-alkoxy, C₁- to C₂₀-alkoxy carbonyl, C₁- to C₂₀-monoalkylaminocarbonyl, formyl, C₁- to C₂₀-alkylcarbonyl, fluorine, chlorine , Bromine, cyano, C₁- to C₂₀-alkylcarbonyloxy, C₁- to C₂₀-alkylcarbo nylamino, hydroxy or nitro.

Die Polymerisation der Gruppen Z wird vorzugsweise photochemisch initiiert. Bevorzugt sind für Z CH₂=CCl- und CH₂=C(CH₃)-.The polymerization of groups Z is preferably photochemical initiated. Preferred for Z are CH₂ = CCl- and CH₂ = C (CH₃) -.

Für Y sind neben einer direkten Bindung insbesondere Ether- und Estergruppen zu nennen.For Y, in addition to a direct bond, ether and To name ester groups.

Als Spacer A können alle für diesen Zweck bekannten Gruppen verwendet werden. Üblicherweise sind die Spacer über Ester- oder Ethergruppen oder eine direkte Bindung mit Z verknüpft. Die Spacer enthalten in der Regel 5 bis 30, vorzugsweise 5 bis 12 C-Atome und können in der Kette z. B. durch O, S, NH oder NCH₃ unterbrochen sein. Als Substituenten für die Spacer­ kette kommen dabei noch Fluor, Chlor, Brom, Cyan, Methyl oder Ethyl in Betracht. Repräsentative Spacer sind beispielsweise (CH₂)p, (CH₂CH₂O)qCH₂CH₂, (CH₂CH₂S)qCH₂CH₂, (CH₂CH₂NH)qCH₂CH₂,All groups known for this purpose can be used as spacer A. The spacers are usually linked to Z via ester or ether groups or a direct bond. The spacers usually contain 5 to 30, preferably 5 to 12 carbon atoms and can in the chain, for. B. be interrupted by O, S, NH or NCH₃. Fluorine, chlorine, bromine, cyan, methyl or ethyl are also suitable as substituents for the spacer chain. Representative spacers are, for example, (CH₂) p , (CH₂CH₂O) q CH₂CH₂, (CH₂CH₂S) q CH₂CH₂, (CH₂CH₂NH) q CH₂CH₂,

wobei q 1 bis 3 und
p 5 bis 20, vorzugsweise 5 bis 12, sind.where q 1 to 3 and
p are 5 to 20, preferably 5 to 12.

Die Substituenten R¹, R² und R³ können Wasserstoff oder die ange­ gebenen Reste sein. Bevorzugt sind solche Reste, die die Ausbil­ dung von smektischen Phasen unterdrücken und die von nematischen Phasen fördern. Vorzugsweise ist einer der R-Reste Wasserstoff. Von den genannten Substituenten sind Chlor, Brom, Cyan, Fluor, Hydroxy, Methyl, Ethyl, Methoxy, Ethoxy, Methoxycarbonyl, Formyl, Acetyl und Acetoxy sowie längerkettige mit ≧8 C-Atomen bevor­ zugt.The substituents R¹, R² and R³ can be hydrogen or the leftovers. Preferred radicals are those which form Suppression of smectic phases and nematic Promote phases. Preferably one of the R groups is hydrogen. Of the substituents mentioned are chlorine, bromine, cyan, fluorine, Hydroxy, methyl, ethyl, methoxy, ethoxy, methoxycarbonyl, formyl, Acetyl and acetoxy as well as longer-chain ones with ≧ 8 C atoms before moves.

Die Herstellung der Verbindungen der Formel I erfolgt nach an sich bekannten Methoden. Einzelheiten zur Herstellung können den Beispielen entnommen werden, in denen sich Angaben über Teile und Prozente, sofern nicht anders vermerkt, auf das Gewicht beziehen. Die Verbindungen der Formel I sind flüssigkristallin und können in Abhängigkeit von der Struktur smektische oder nematische Phasen ausbilden. Sie sind für alle Zwecke geeignet, bei denen man üblicherweise flüssigkristalline Verbindungen verwendet.The compounds of the formula I are prepared according to known methods. Details of the manufacture can Examples are taken, in which information about parts and Unless otherwise noted, percentages are based on weight. The compounds of formula I are liquid crystalline and can depending on the structure smectic or nematic Train phases. They are suitable for all purposes where liquid crystalline compounds are usually used.

Die erfindungsgemäßen Verbindungen weisen allein, in Mischungen untereinander oder gemischt mit anderen flüssigkristallinen Verbindungen Phasenstrukturen wie niedermolekulare Flüssigkri­ stalle auf, lassen sich jedoch durch radikalische oder ionische Polymerisationsverfahren, welche durch eine photochemische Reak­ tion gestartet werden können, in hochvernetzte Polymere mit ein­ gefrorener flüssigkristalliner Ordnungsstruktur überführen.The compounds of the invention alone, in mixtures with each other or mixed with other liquid crystalline ones Compounds phase structures like low molecular weight liquid crystals stall, but can be by radical or ionic Polymerization process, which by a photochemical Reak tion can be started in highly crosslinked polymers transfer frozen liquid crystalline order structure.

Zur Einstellung gewünschter Eigenschaften kann es zweckmäßig sein, Mischungen von Verbindungen der Formel I oder Mischungen mit anderen Flüssigkristallen oder auch nicht flüssigkristallinen Verbindungen zu verwenden.It can be useful for setting desired properties be mixtures of compounds of formula I or mixtures with other liquid crystals or not liquid crystal To use connections.

Die erfindungsgemäßen Verbindungen eignen sich insbesondere als Orientierungsschichten für flüssigkristalline Materialien, als photovernetzbare Kleber, als Monomere zur Herstellung flüssig­ kristalliner Netzwerke, als Basismaterial zur Herstellung von chiral dotierbaren polymerisierbaren Flüssigkristallsystemen, als polymerisierbare Matrixmonomere für polymer dispergierte Displays oder als Basismaterial für polymerisierbare, flüssigkristalline Materialien für optische Bauelemente, wie Polarisatoren, Ver­ zögerungsplatten oder Linsen. Sie sind weiterhin Ausgangs­ materialien zur Herstellung flüssigkristallin geordneter Farb­ mittel.The compounds according to the invention are particularly suitable as Orientation layers for liquid crystalline materials, as Photo-crosslinkable adhesive, as a monomer for the production of liquid crystalline networks, as base material for the production of chirally doped polymerizable liquid crystal systems, as polymerizable matrix monomers for polymer dispersed displays or as a base material for polymerizable, liquid crystalline Materials for optical components, such as polarizers, Ver delay plates or lenses. You are still starting  materials for the production of liquid-crystalline ordered color medium.

BeispieleExamples

Die Schmelztemperaturen wurden polarisationsmikroskopisch aufge­ nommen. Die Temperaturkontrolle erfolgte in einem Mettler Mikro­ skopheiztisch FP80/82.The melting temperatures were measured using polarization microscopy taken. The temperature was checked in a Mettler micro Scope heating table FP80 / 82.

Im folgenden bedeuten die AbkürzungenIn the following, the abbreviations mean

k kristalline Phase
n nematische Phase
i isotrope Phase.k crystalline phase
n nematic phase
i isotropic phase.

Beispiel 1example 1

Herstellung vonProduction of

a) Herstellung von 4-(ω-Hydroxyhexyloxy)-benzoesaureethylestera) Preparation of ethyl 4- (ω-hydroxyhexyloxy) benzoate

166 g (1 mol) 4-Hydroxybenzoesäureethylester werden in 400 ml DMF gelöst. Zu dieser Lösung werden 150 g Kaliumcarbonat, 6 g Kaliumjodid und 150 g 1-Chlor-6-hydroxyhexan gegeben, danach wird 5 h bei 80 bis 90°C gerührt. Der Fortgang der Reaktion wird dünnschichtchromatografisch verfolgt. Nach vollständigem Umsatz wird das Reaktionsgemisch in 2 l Wasser eingerührt, das ausgefallene Produkt abgesaugt und mit Wasser gewaschen. Zur Reinigung wird aus ca. 2,5 l Cyclohexan umkristallisiert.
Ausbeute: 201 g (75,5% d.Th.)166 g (1 mol) of 4-hydroxybenzoic acid ethyl ester are dissolved in 400 ml of DMF. 150 g of potassium carbonate, 6 g of potassium iodide and 150 g of 1-chloro-6-hydroxyhexane are added to this solution, and the mixture is then stirred at 80 to 90 ° C. for 5 h. The progress of the reaction is monitored by thin layer chromatography. After conversion is complete, the reaction mixture is stirred into 2 l of water, the precipitated product is filtered off with suction and washed with water. For cleaning, it is recrystallized from approx. 2.5 l of cyclohexane.
Yield: 201 g (75.5% of theory)

b) Herstellung von 4-(ω-Hydroxyhexyloxy)-benzoesäureb) Preparation of 4- (ω-hydroxyhexyloxy) benzoic acid

199 g (0,75 mol) 4-(ω-Hydroxyhexyloxy)-benzoesäureethylester und 56 g (1 mol) Kaliumhydroxid werden in 1 l Ethanol gelöst und 4 Stunden unter Rückfluß erhitzt. Zur Aufarbeitung wird das Reaktionsgemisch mit konzentrierter Salzsäure angesäuert und der ausgefallene Feststoff abfiltriert, mit Wasser gewa­ schen und getrocknet. Anschließend wird aus Toluol/Ethanol (4/1) umkristallisiert.
Ausbeute: 165 g ( 92% d.Th.).199 g (0.75 mol) of ethyl 4- (ω-hydroxyhexyloxy) benzoate and 56 g (1 mol) of potassium hydroxide are dissolved in 1 liter of ethanol and heated under reflux for 4 hours. For working up, the reaction mixture is acidified with concentrated hydrochloric acid and the precipitated solid is filtered off, washed with water and dried. The mixture is then recrystallized from toluene / ethanol (4/1).
Yield: 165 g (92% of theory).

c) Herstellung von 4-(ω-Chloracryloxyhexyloxy)-benzoesäurec) Preparation of 4- (ω-chloroacryloxyhexyloxy) benzoic acid

160 g (0,67 mol) 4-(ω-Hydroxyhexyloxy)-benzoesäure, 108 g (1,5 mol) Acrylsäure und 5 g Paratoluolsulfonsäure werden in 900 ml Toluol gelöst und bis zur Beendigung der Wasser­ abscheidung zum Rückfluß erhitzt. Zur Aufarbeitung wird das Reaktionsgemisch auf Wasser gegeben, der ausgefallene Fest­ stoff abfiltriert und mit Wasser von Acrylsäure frei gewa­ schen, anschließend getrocknet, und aus Ethanol um­ kristallisiert.
Ausbeute: 182 g ( 92% d.Th.).160 g (0.67 mol) of 4- (ω-hydroxyhexyloxy) benzoic acid, 108 g (1.5 mol) of acrylic acid and 5 g of paratoluenesulfonic acid are dissolved in 900 ml of toluene and heated to reflux until the water has stopped separating. For working up, the reaction mixture is poured onto water, the precipitated solid is filtered off and washed free of acrylic acid with water, then dried and recrystallized from ethanol.
Yield: 182 g (92% of theory).

d) Herstellung von 4-(ω-Chloracryloxyhexyloxy)-benzoesäure­ chloridd) Preparation of 4- (ω-chloroacryloxyhexyloxy) benzoic acid chloride

180 g 4-(ω-Acryloxyhexyloxy)-benzoesäure werden in 700 ml Oxalylchlorid gelöst und mit 1 ml Dimethylformamid versetzt. Die Reaktionsmischung wird dann über Nacht bei Raumtemperatur gerührt und danach zunächst unter Wasserstrahlvakuum und an­ schließend unter Ölpumpenvakuum bei Raumtemperatur eingeengt.
Ausbeute: 189 g.180 g of 4- (ω-acryloxyhexyloxy) benzoic acid are dissolved in 700 ml of oxalyl chloride and 1 ml of dimethylformamide is added. The reaction mixture is then stirred overnight at room temperature and then concentrated first under a water jet vacuum and then under an oil pump vacuum at room temperature.
Yield: 189 g.

e) Herstellung von Bis-1,4-[4′-(4′′-Chloracryloxyhexoxy)-benzoyl­ oxy]-benzole) Preparation of bis-1,4- [4 '- (4' '- chloroacryloxyhexoxy) benzoyl oxy] benzene

In 100 ml Pyridin werden 11,4 g (0,1 mol) Hydrochinon gelöst. Bei Raumtempertur wird langsam eine Lösung von 72,2 g (0,21 mol) 4-(ω-Chloracryloxyhexoxy)-benzoesäurechlorid in 100 ml Toluol zugetropft. Nach vollständiger Zugabe wird die Reaktionsmischung auf 60°C erhitzt und bei dieser Temperatur 4 h gerührt. Der Fortgang der Reaktion wird dünnschichtchro­ matografisch verfolgt. Nach Beendigung der Reaktion wird wie üblich aufgearbeitet.
Ausbeute: 54,1 g ( 82% d.Th.)
Phasenverhalten: k 86 n 104 i.11.4 g (0.1 mol) of hydroquinone are dissolved in 100 ml of pyridine. At room temperature, a solution of 72.2 g (0.21 mol) of 4- (ω-chloroacryloxyhexoxy) benzoic acid chloride in 100 ml of toluene is slowly added dropwise. After the addition is complete, the reaction mixture is heated to 60 ° C. and stirred at this temperature for 4 h. The progress of the reaction is monitored by thin-layer chromatography. After the reaction is worked up as usual.
Yield: 54.1 g (82% of theory)
Phase behavior: k 86 n 104 i.

Claims (8)

1. Polymerisierbare, flüssigkristalline Verbindungen der allge­ meinen Formel I in der die Reste
Z unabhängig voneinander eine polymerisierbare Gruppe der Struktur CH₂=CCl-, CH₂=C (CH₃)- oder Styryl,
Y unabhängig voneinander eine direkte Bindung, -O-, -COO-, -OCO- oder -S-,
A unabhängig voneinander einen Spacer mit 5 bis 30 C-Atomen, in denen jedes dritte C-Atom durch O, S, NH, N(CH₃) oder COO ersetzt sein kann und
R¹,R² und R³ unabhängig voneinander Wasserstoff, C₁- bis C₂₀-Alkyl, C₁- bis C₂₀-Alkoxy, C₁- bis C₂₀-Alkoxy­ carbonyl, C₁- bis C₂₀-Monoalkylaminocarbonyl, Formyl, C₁- bis C₂₀-Alkylcarbonyl, Fluor, Chlor, Brom, Cyan, C₁- bis C₂₀-Alkylcarbonyloxy, C₁- bis C₂₀-Alkylcarbonylamino, Hydroxy oder Nitro bedeu­ ten.1. Polymerizable, liquid-crystalline compounds of general formula I in which the leftovers
Z independently of one another is a polymerizable group of the structure CH₂ = CCl-, CH₂ = C (CH₃) - or styryl,
Y independently of one another is a direct bond, -O-, -COO-, -OCO- or -S-,
A independently of one another a spacer with 5 to 30 carbon atoms, in which every third carbon atom can be replaced by O, S, NH, N (CH₃) or COO and
R¹, R² and R³ independently of one another hydrogen, C₁- to C₂₀-alkyl, C₁- to C₂₀-alkoxy, C₁- to C₂₀-alkoxy carbonyl, C₁- to C₂₀-monoalkylaminocarbonyl, formyl, C₁- to C₂₀-alkylcarbonyl, fluorine, chlorine , Bromine, cyan, C₁- to C₂₀-alkylcarbonyloxy, C₁- to C₂₀-alkylcarbonylamino, hydroxy or nitro mean. 2. Polymerisierbare flüssigkristalline Verbindungen gemäß An­ spruch 1, bei denen die Reste Y unabhängig voneinander eine direkte Bindung, -O-, -COO- oder -OCO- sind. 2. Polymerizable liquid-crystalline compounds according to An saying 1, in which the radicals Y independently of one another direct bond, -O-, -COO- or -OCO-.   3. Polymerisierbare flüssigkristalline Verbindungen gemäß An­ spruch 1, bei denen die Reste A unabhängig voneinander gege­ benenfalls durch Ethersauerstoff oder Estergruppen unterbro­ chenes C₅- bis C₂₀-Alkylen sind, wobei die Sauerstoffatome oder Estergruppen in der Kette dritte C-Atome ersetzen kön­ nen.3. Polymerizable liquid-crystalline compounds according to An Proverb 1, in which the residues A against each other interrupted if necessary by ether oxygen or ester groups Chenes are C₅ to C₂₀ alkylene, the oxygen atoms or ester groups in the chain can replace third carbon atoms nen. 4. Polymerisierbare flüssigkristalline Verbindungen gemäß An­ spruch 1, bei denen R¹, R² und R³ unabhängig voneinander Was­ serstoff, C₁ bis C₁₅-Alkyl, C₁- bis C₁₅-Alkoxy, C₁- bis C₁₅-Alkoxycarbonyl, C₁- bis C₁₅-Monoalkylaminocarbonyl, Formyl, C₁- bis C₁₅-Alkylcarbonyl, Fluor, Chlor, Brom, Cyan, C₁- bis C₁₅-Alkylcarbonyloxy, C₁- bis C₁₅-Alkylcarbonylamino, Hydroxy oder Nitro bedeuten.4. Polymerizable liquid-crystalline compounds according to An claim 1, in which R¹, R² and R³ independently of each other What serstoff, C₁ to C₁₅-alkyl, C₁- to C₁₅-alkoxy, C₁- bis C₁₅ alkoxycarbonyl, C₁ to C₁₅ monoalkylaminocarbonyl, Formyl, C₁ to C₁₅ alkylcarbonyl, fluorine, chlorine, bromine, cyan, C₁ to C₁₅ alkylcarbonyloxy, C₁ to C₁₅ alkylcarbonylamino, Hydroxy or nitro mean. 5. Polymerisierbare flüssigkristalline Verbindungen gemäß An­ spruch 4, bei denen R¹, R² und R³ unabhängig voneinander Was­ serstoff, Methyl, Ethyl, C₈ bis C₁₅-Alkyl, Methoxy, Ethoxy, C₈- bis C₁₅-Alkoxy, Methoxycarbonyl, Ethoxycarbonyl, C₈- bis C₁₅-Alkoxycarbonyl, Formyl, Acetyl, C₈- bis C₁₅-Alkylcarbonyl, Fluor, Chlor, Brom, Cyan, Acetoxy, Hydroxy oder Nitro sind.5. Polymerizable liquid-crystalline compounds according to An saying 4, in which R¹, R² and R³ independently of one another What serstoff, methyl, ethyl, C₈ to C₁₅ alkyl, methoxy, ethoxy, C₈- to C₁₅ alkoxy, methoxycarbonyl, ethoxycarbonyl, C₈- bis C₁₅ alkoxycarbonyl, formyl, acetyl, C₈ to C₁₅ alkylcarbonyl, Are fluorine, chlorine, bromine, cyan, acetoxy, hydroxy or nitro. 6. Polymerisierbare flüssigkristalline Verbindungen gemäß An­ spruch 5, bei denen R¹, R² und R³ unabhängig voneinander Was­ serstoff, Methyl, Ethyl, Methoxy, Ethoxy, Methoxycarbonyl, Formyl, Acetyl, Fluor, Chlor, Brom, Cyan, Acetoxy, Hydroxy oder Nitro sind.6. Polymerizable liquid-crystalline compounds according to An Proverb 5, in which R¹, R² and R³ independently What serstoff, methyl, ethyl, methoxy, ethoxy, methoxycarbonyl, Formyl, acetyl, fluorine, chlorine, bromine, cyan, acetoxy, hydroxy or are nitro. 7. Verwendung der Verbindungen gemäß Anspruch 1 bis 6 als Orien­ tierungsschichten für flüssigkristalline Materialien, als photovernetzbare Kleber, als Monomere zur Herstellung flüssigkristalliner Polymere, als Basismaterial zur Herstel­ lung von chiral dotierbaren polymerisierbaren Flüssig­ kristallsystemen, als polymerisierbare Matrixmonomere für polymer dispergierte Displays oder als Basismaterial für po­ lymerisierbare, flüssigkristalline Materialien für optische Bauelemente.7. Use of the compounds according to claims 1 to 6 as orien tion layers for liquid crystalline materials, as Photo-crosslinkable adhesives, as monomers for production liquid crystalline polymers, as base material for the manufacture chirally doped polymerizable liquid crystal systems, as polymerizable matrix monomers for polymer dispersed displays or as base material for po Lymerizable, liquid crystalline materials for optical Components. 8. Verwendung der Verbindungen gemäß Anspruch 1 bis 6 zur Her­ stellung cholesterisch flüssigkristallin geordneter Farb­ mittel.8. Use of the compounds according to claims 1 to 6 for the preparation position cholesteric liquid crystalline ordered color medium.
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